Mixed phases with a rutile or polyrutile structure



United States Patent 6 This invention relates to mixed or solid solutions with a rutile or polyrutile structure.

It is known to heat titanium dioxide, especially anatase and also the hydrox de forms of 4-valent titanium, with the addition of difierent metal oxides or salts, partly in order to favour the conversion of anatase to rutile,

partly in order to improve the pigment properties of white titanium dioxide and partly to produce coloured pigments. Thus, for example, oxides or salts of lithium, sodium, potassium, copper, beryllium, magnesium, calcium, strontium, barium, zinc, boron, aluminium, cerium, titanium (III), antimony (III), vanadium (III), chro' mium (HI), manganese (III), rhodium (III), silicon, zirconium, antimony (V), vanadium (V), chromium (VI), tungsten (VI), uranium (VI) manganese (VII), cobalt, nickel and iron have been added in greater or lesser amounts, single or as mixtures of two or more such compounds, to titanium (IV) compounds during calci'nation. With the exception of those cases where such addition is made to simplify rutile formation and where it is a question only of a small addition of colourless components, all previous processes yield products I which are crystallographically more or less undefined or indefineable. These known processes have been carried out arbitrarily with regard to such additions, not only in a qualitative but also in a quantitative respect.

Small quantities of oxides of vanadium and/or molybdenum, or of such compounds of these elements as are capable of changing under treatment or on heating into oxides, have already been added to tin dioxide and to zirconium dioxide or their mixtures, and the mixtures have been heat-treated in order to produce yellow pigments for ceramic and enamel purposes. As with the processes using titanium dioxide which have already been mentioned, the additives were in this case also chosen quite arbitrarily both with regard to quantity and quality so that no definite structure or high quality pigments were formed.

It has now been found that geniune mixed phases with a. rutile or polyrutile structure are obtained by using as host components metal-oxygen or metal-fluorine compounds generally forming rutile or polyrutile lattices and incorporating into them as additional or guest components such metal oxides and/or fluorides the cations of which possess radii which are comparable with the radii of the metal ions or the statistical mean of the radii of the metal ions of the host components. The additional components are incorporated in such proportions relative to one another that the ratio of the sum of the added cations to the sum of the added anions, while preserving statistical electroneutrality in the lattice, is substantially 1:2. The total proportion of the additional components may on the other hand he of any desired value, but the amount is preferably not greater than approximately the total amount of the host components.

Such genuine mixed phases constitute white or coloured pigments which are particularly outstanding as regards their pigment properties, and more especially their colour intensity, as compared with all prior known mixed products with a rutile or polyrutile structure.

3,022,186 Patented Feb. 20, 1962 As is known, in the simplest case the rutile lattice consists of a tetragonal elementary cell with two molecules of specific metal dioxides or difiuorides, the oxygen or fluorine ions being arranged in a distorted octahedron around the metal ions. By a suitable combination of trivalent and pentavaleut metal oxides instead of .dioxides, however, rutile lattices in which the two metal ions of different valency are statistically distributed are formed. Representatives of this group are for example antimonates, tantalates, niobates and vanadates of certain trivalent metals. Finally, a trirutile or polyrutile lattice, instead of the normal rutile lattice is formed by combining a suitable monova-lent or divalent metal oxide with three molecules and one molecule, respectively, of metal pentoxide. In this case, a subordinate distribution of the monovalent or divalent and pentavalen-t metal ions takes place with trebling or multiplication of the c-axis of the tetragonal cell.

Host components which form rutile or polyrutile lattices include in particular the following:

TiO and S as well as AlSbO GaSbO VSbO CfSbO,, -FeSbO and RhSbO LiSb O MgSb O ZfiSbzGe, Fesbzoe, COSb O CuSb O also BMHOZ, Pbsg, V02, 6e02, T602, CI'OZ, R110 0502, 11:02, CrTaO FeTaO ,'RhTaO CrNbO.,, FeNbo RhNb0 RhVO, and MgF ZnF MnF FeF CoF NiF ldF as well as Mg'fa O NiTa O Co'fa O FeTa O I The radii of the metal ions of these various host com- (LiSb (XVI) =O.66 A., (MgSb (XII) =0.67 A., (ZnSb (XII) =-0.69 A., (.FeSb (XII) =0.69 A., (C0Sb (XII) =0.69 A., (NiSb (x11 =05? A., cusbz) (X11 =0.65 A., (AlSb) V111 =0.60 A., (GaSb) V111 =O.62 A., (VSb) (VIII) =O.64 A., (CrSb) V111 =0.63 A., (FeSb) V111 =0.65 A., (RhSb) (VIII) =-0.65 A., (CrTa) (VIII) =0.66 A., (FeTa) (VIII)=().68 A., (RhTa) (VIII) =0.68 A., (CrNb) (VIII)=0.67 A., (FeNb) (VIII) =0.68 A., (RhNb) (VIII) ,=0.69 A., (RhV) (VIII) =O.64 A., (MgTaz) (XII) =0.71 A., (NiTaz) (XII)=0 .71 A., CoTa x11 =0.73 A., (FeTa x11 0.73 A.

By proceeding .in accordance with the requirements specified above, it is now possible according to my invention to incorporate into host components forming the said rutile or polyrutile lattices those metal oxides and/ or fluorides the cations of which possess radii which are in every case comparable with the radii of the metal ions or the statistical mean of the radii of the metal ions of the host components. Examples of metal oxides and fluorides of this type are those of lithium, magnesium, zinc, manganese (II) ion radius=0.91 A., iron (II), cobalt (II), nickel (II), vanadium (II) (for ion radii, see

above), copper (II), (ion radus=0.72 A.), aluminium (ion radius=0.57 A.), gallium (ion radius=O.62 A.), titanium (III), (ion -radius=0.69 A.), arsenic (III) (ion radius=0.69 A.), antimony (III) (ion radius=0.90 A.), vanadium (III) (ion radius=0.65 A.) niobium (III) (ion radius 0.69 A.), tantalum (III) (ion radius 068 A.), chromium (III) (ion radius=0.64 A.), manganese (III) (ion radius=0.70 A.), iron (III) (ion radius ='O.67 A.), rhodium (III) (ion radius=0.68 A.), ger- V manium' (IV), lead (IV), vanadium (IV), tellurium (IV), chromium (IV), ruthenium (IV), osmium (IV), iridium (IV), (for ion radii, see above), tin (IV) (ion radius=0.74 A.), zirconium (IV) (ion radius=0.87 A.), hafnium (IV) (ion radius=0.84 A.), antimony (V) (ion radius=0.62 A.), bismuth (V) (ion radius=0.74 A.), vanadium (V) (ion radius=0.59 A.), niobium (V) (ion radius=0.69 A.), tantalum (V) (ion radius=0.68 A.), molybdenum (VI) (ion radius=0.62 A.), tungsten (VI) (ion radlus=0.62 A.), uranium (VI) (ion radius=0.8 A.) and tellurium '(VI) (ion radius=0.56

Metal compounds such as those of sodium, potass um, beryllium, calcium, strontium, barium, boron, silicon, cerium (IV), chromium (VI) and manganese (VII), which have also previously been added to, for example, titanium oxide, are not to be considered for use in making genuine mixed phases according to the invention since, even apart from their probable unfavourable thermostability, their ion radii are not comparable with those of the host components.

Examples of combinations of additional components to be used for forming the mixed phases according to the invention and which satisfy the requirement that the ratio of the sum of the added cations shall be substantially 1:2, to the sum of the added anions, while preserving statistical electroneutrality on the lattice, are one molecule of arsenic (V)-, antimony (V)- and/or bismuth (V)- and/or niobium (V)- and/or tantalum (V)- and/or 1 molecule of molybdenum (VI)- and/or tungsten (VI)- and/or uranium (VI)- and/or tellurium (VD-oxides to 1 molecule of nickel (lI)-, cobalt (II)-, magnesium-, zinc-, manganese (II)-, iron (II) or copper (ID-oxides, or 1 molecule of arsenic (V), antimony (V) and/or bismuth (V)- and/or niobium (V)- and/or and/or hafnium (IV)-oxides to 1 molecule of lithium oxide. The monovalent, divalent, trivalent and tetravalent oxides of the said types canbe combined in any desired manner with the said pentaor hexavalent oxides. In all cases, it is however necessary to satisfy the requirement that the ratio of the sum of the added cations to the sum of the added anions shall be substantially 1:2, while preserving statistical electroneutralty in the lattice. 1. Furthermore, mixed phases can, for example, consist of titanium dioxides or tin dioxide and the difluorides of divalent metals, for example Mg, Zn, Mn(II), Fe(II), Co(II), Ni(II) or Cu(II). In this case, with the exception of CuF the added difluorides crystallise in the rutile lattice. The said difluorides can be incorporated singly, severally or all together into the rutile lattice.

Other mixed phases can, moreover, be formed using mixtures of equimolecular parts of a trifluoride and of a fluoride of a monovalent metal, for example AlF -l-LiF,

guest or additional components.

'then 3Cr ++2Li i.e. 5 cations, and 9F "+1O i.e.

l0 anions, enter the lattice. The sum of the incorporated cation charges is +11, the sum of the anion charges introduced is 11, and therefore statistical electroneutrality is preserved. Suitable trifluorides for this form of incorporation are AlF GaF CrF MnF and RE. The separate trifluorides can be used alone, severally or all simultaneously for incorporation into the host lattice.

Further, mixed phases can, for example, consist of the host component and a mixture of equimolecular parts of a trifluoride and a divalent metal oxide, for example the combinat'on of lFeF and 12110; in this example lFe and lZn' (=2 cations) and SF- and 10 (=4 anions) simultaneously enter the host lattice; the sum of the cation charge introduced is +5 and that of the anion charge is -5, and therefore statistical electroneutrality is preserved. The trifluorides are the same as those mentioned above; examples of suitable metal oxides are the ox'des of Mg, Zn, Mn(II), Fe(II), Co(II), Ni(Ii) and Cu(II). The trifluorides and the divalent metal oxides can be used singly or in combination without the mixed phase being changed in its crystal structure. Furthermore, mixed phases can be obtained using an equimolecular mixture of metal trifluoride and trivalent metal oxide as additional components. The system CrF +Cr O is to be mentioned as a simple example of this type of incorporation; in this example 3Cr (=3 cations) and 3F and 30 (:6 anions) simultaneously enter the lattice. The sum of the entering cation charges is=+9 and the corresponding sum of the anion charges is -9. Statistical electroneutrality thus prevails in this case also. Trifluorides, which can be considered for use are again those mentioned above; the trivalent metal oxides contain the same metals as those of the said trifluorides. The trifluoridescan each individually or all together be combined with one individual sesquioxide, or with all the sesquioxides, the corresponding rutile phase nevertheless being maintained. 7

Other mixed phases can contain an equimolecular mixture of pentavalent metal oxides and monovalent metal fluoride. In the case of the mixture of Sb O with UP, 2% and lLi (=3 cations and 50 and one F (-=6 anions) simultaneously'enter the lattice. The sum of the cation charges introduced is +11 and that of the anion charges is l1; statistical electroneutrality thus prevails in this case also. Examples of other suitable pentavalent metal oxides for incorporation are the pentoxide of arsenic, antimony, bismuth, vanadium, niobium and tantalum. 7 Here also, one, some or all of the aforementioned pentoxides can be combined with lithium fluoride.

Further mixed phases can consist of, for example, the host component and an equimolecular mixture or hexavalent metal oxide and monovalent metal fluoride. A simple example of these additives is the system W0 and UP. In this case 1W and 1Li (=2 cations) and 30 and lF (=4 anions) simultaneously enter the host lattice as additional substances or guests. The sum of the entering cation charges is +7 and that of the entering anion charges is -7; statistical electroneutrality therefore prevails. Examples of trioxides which can be considered are those of molybdenum, tungsten, uranium and tellurium. Here also, the different trioxides can be combined singly or in combination with lithium fluoride.

Finally, we would mention mixed phases with acombination of one or more or all of the individual guest systems. The large possibilities of variation set out in detail are particularly increased in that some or all of the large series of variations referred to above can themselves be combined one with another and in spite of this large number of possible variations, a mixed phase is always formed in the structure of the rutile or polyrutile.

How very important it is to keep as accurately as possible to the rule that the sum of the added cations bears a ratio substantially of 1:2 to the sum of the added anions, while preserving a statistical electroneutrality in the lattice, can be shown from the following example:

If 5.0 grams Ti (as TiCl and 0.5 gram NiO (as Ni(NO are added to difierent amounts of Sb O' (as SbCl solution), (i.e. 2.166 grams Sb O corresponding exactly to the ratio NiO:Sb O =1:1), followed by 0.05 gram NaF (fiuidising agent), and the mixture then evaporated and calcined by heating to 800-1200" C., lemon yellow pigments are obtained whose colour strengths as measured by rubbing with synthetic barium sulphate are as follows.

Molar raito of NiO:Sb O Colour strength Thus, if the amounts of the two or more 5- and/or 6- and 3-, 2- and/or l-valent metal oxides or fluorides which can be contained in the mixed phases as additional components are co-ordinate relatively with one another, then the ratio of the titanium dioxide component to the total additional components can vary Within wide limits. Nevertheless, in general, a content of the total additional components of between about 0.5 and about 50 percent is of special interest.

The production of the mixed phases, in principle, proceeds in that a mixture of the components are converted into the mixed phases at elevated temperatures, particularly at red heat. In this case, heat labile compounds of the various metals, instead of the oxide components can be used, which compounds are converted by heating into the components of the mixed phase. Thus, for example, the hydrate of titanium dioxide can be used instead of titanium dioxide and is converted by heating into this dioxide. Instead of the oxides of the metals, such for example as magnesium oxide or zinc oxide, their hydroxides, carbonates, acetates, nitrates or formates can for example be used. If desired, small amounts of a fluidising agent, such as lithium or sodium fluoride, can be added to the mixtures in order to simplify the formation of mixed crystals.

When using as initial components metal compounds of low valency which are to maintain this valency in the final product, i.e. in the mixed phase, it can be necessary to carry out the heating mixture in an inert gas atmosphere with the exclusion of oxygen.

The following examples describe the production of typical representatives of the new mixed phasesaccording to the invention:

EXAMPLE 1 5.000 grams of anatase+0.020 gram of Li O (calculated from Li CO )+0.466 gram of W0 (calculated from H WO are well mixed, calcined for half an hour at 800 C. and, after further pulverising, for half an hour at 1000" C. A white to light. grey pigment which, according to X-ray analysis, has a rutile structure is obtained.

EXAMPLE 2 5.000 grams of anatase+0.050 gram of MgO (calculated from MgCO +0.288 gram of WO; (calculated from H WO are well mixed, calcined for halt an hour at 800 C. and, after further pulverising, for half an hour at 1000 C. A white to greenish grey-white pigment which, according to X-ray analysis, has a rutile structure is obtained.

EXAMPLE 3 5.000 grams of anatase+0.200 gram of ZnO (calculated from ZnCO )+0.570 gram of W0 (calculated from H WO are well mixed, calcined for half an hour at 800 C. and, after further pulverising, for half an hour at 1000 C. A yellowish-White pigment having the crystal structure of rutile is obtained.

EXAMPLE 4 5.000 grams of anatase+0.200 gram of A1 0 (calculated from active aluminium oxide hydrate) +0455 gram of W0 (calculated from H WO are well mixed, calcined for half an hour at 800 C. and, after further pulverising, for half an hour at 1000 C. A grey white pigment of rutile structure is obtained.

EXAMPLE 5 5.000 grams of anatase+0.200 gram of MnO (calculated from MnCO )+0.654 gram of W0 (calculated from H WOQ are well mixed, calcined for half an hour at 800 C. and, after further pulverising, at 1000 C. A dark red-brown pigment which, according to X-ray analysis, has a rutile structure is obtained.

EXAMPLE 6 5.000 grams of anatase+0.500 gram of FeO (calculated from FeCO )+1.6l5 grams of W0 (calculated from H WO are well mixed, calcined for half an hour at 800 C. and, after further pulverising, for half an hour at 1000 C. An olive green pigment which, according to X-ray examination, has a rutile structure is obtained.

EXAMPLE 7 5.000 grams of anatase+0.200 gram of C00 (calculated from CoCO )+0.620 of W0 (calculated from H WO are Well mixed, calcined for half an hour at 800 C. and, after further pulverising, for half an hour at 1000 C. A reddish light brown pigment which has a rutile structure is obtained.

EXAMPLE 8 5.000 grams of anatase+0.200 gram of NiO (calculated from NiCO )+0.620 gram of W0 (calculated from H WO are Well mixed, calcined for-half an hour at 800 C. and, after further pulverising, for half an hour at 1000" C. A beautiful and completely canary yellow pigment having a rutile structure is obtained.

EXAMPLE 9 5.000 grams of anatase+0.100 gram of Ni() (calculated from NiCO )-|-0.310 gram of W0 (calculated from H WO )+0.050 gram of NaF are well mixed, calcined for half an hour at 800 C. and, after further pulverising, for half an hour at 1000 C. A full clean bright canary-yellow pigment having the structure of rutile is obtained.

EXAMPLE 10 5.000 grams of anatase+0.500 gram of CuO (calculated from CuCO )+1.450 grams of W0 (calculated from H WO are well mixed, calcined for half an hour at 800 C. and, after further pulverising, for half an hour at 1000 C. A dark olive-coloured pigment of the rutile type is obtained.

EXAMPLE 11 5.000 grams of anatase+0.100 gram of CuO (calculated from CuCO )+0.290 gram of W0 (calculated from H WO are Well mixed, calcined for half an hour at 800 C. and, after further pulverising, for half an hour at 1000 C. A pale green pigment having a rutile structure is obtained.

' EXAMPLE 12 5.000 grams of anatase+0.200 gram of Cr O +0.306 gram of W (calculated from H WO are well mixed, calcined for half an'hour at 800 C. and, after further pulverising, for half an hour at 1000 C. A brownorange pigment which, according to X-ray analysis, has

a rutile structure is obtained.

EXAMPLE 13 5.000 grams of anatase+0.100 gram of MnO (calculated from MnCO )+0.1636 gram of W0 (calculated from H WO are mixed well, calcined for half an hour at 800 C. and, after further pulverising, for half an hour at 1000 C. A pale pink to reddish brown pigment having the structure of rutile is obtained.

EXAMPLE 14 5.000 grams of anatase+0.500 gram of Fe O +0.726 gram of W0 (calculated from H WO are mixed'well, calcined for half an hour at 800 C. and, after further pulverising, for half an hour at 1000 C. A yellowish V pale green pigment having a rutile structure is obtained.

EXAMPLE 15 5.000 grams of anatase+0.200 gram of NiO'(ca1culated from NiCO )+0.347 gram of Sb O +0.372 gram of W0 (calculated from H WO +0.200 gram of NaF are mixed well, calcined for half an hour at 800 C.

and, after furtherpulverising, for half an hour at 1000' C. A canary-yellow pigment is obtained having the crystal structure of rutile.

EXAMPLE l6 5.000 grams of anatase+0.200 gram of MO (cal- V culated from NiCO )+0.l95 gram of V 0 (calculated from NH VO )+0.372 gram of W0 (calculated from H WO +0200 gram of NaF are mixed well, calcined for half an hour at 800 C. and, after further pulverising, for half an hour at 1000 C. An orange pigment which has a dirty greenish cast and which, according to X-ray analysis, has a rutile structure is obtained.

EXAMPLE 17 5.000 grams of anatase+0.200 gram of CuO (calculated from CuCO +0.487 gram of Sb O +0.233 gram of W0 (calculated from H WO are mixed Well, calcined for half an hour at 800 C. and, after further pulversing, for half an hour at 1000 C. A dirty pale green pigment having a rutile structure is obtained.

EXAlVIPLE 18 5.000 grams of anatase+0.200 gram of CuO (calculated from CuCO )+0.l83 gram of V 0 (calculated from NH VO +0350 gram of W0 (calculated from HgWO are well mixed, calcined for half an hour at 800 C. and, after further pulverising, for half an hour at 1000 C. A medium brown pigment having the crystal structure of rutile is obtained.

EXAMPLE 19 5.000 grams of anatase+0.050 gram of CuO (calculated from CuCO )+0.050 gram 'of 'NiO (calculated fiom NiCO )+0.300 gram of W0 (calculated from H WO are well mixed, calcined for half an hour at 800 C. and, after further pulverising, for half an hour at 1000 C. A yellow pale green pigment with the crystal structure of rutile is obtained.

EXAMPLE 20 v 5.000 grams of anatase+0.l00 gram of C00 (calculated from CoCO )+0.l00 gram of NiO (calculated from NiCO )+0.620 gram of W0 (calculated from H WO are well mixed, calcined for half an hour at r 3 800 C. and, after further pulverising, for half an hour at 1000 C. An orange pigment having the structure of rutile is obtained. 7

EXAMPLE 21 5.000 grams of anatase+0.l00 gram of NiO (calculated from NiCO +0100 gram of Cr O +0.463 gram of W0 (calculated from H WO are mixed well, calcined for half an hour at 800 C. and, after further pulverising, for half an hour at 1000 C. An orange pigment with a brownish cast and having a rutile structure is obtained.

EXAMPLE 22 7 5.000 grams of anatase+0.l00 gram of NiO (calculated from NiCO )+0.100 gram of CuO (calculated from CuCO )+0.433 gram of Sb O +0.290 gram of W0 (calculated from H WO are Well mixed, calcined for half an hour at 800 C. and, after further pulverising, for half an hour at 1000 C. A pale green pigment which, according to X-ray analysis, has a rutile structure is obtained.

EXAMPLE 23 5.000 grams of anatase+0.200 gram of NiO (calculated from NiCO )+0.200 gram of NaF+0.500 gram of Bi O (calculated from Bi O )+0.372 gram of W0 (calculated from H WO are well mixed, calcined for half an hour at 800 C. and after further pulverising,

for half an hour at 1000 C. A canary-yellow pigment with a rutile structure is obtained.

EXAMPLE 24 5.000 grams of anatase+0.500 gram of MO (calculated from NiCO )+1.1 63 grams of WO;., (calculated from H WO +0.479 gram of U0 (calculated from uranyl nitrate) are well mixed, calcined for half an hour at 800 C. and, after further pulverising, for half an hour at 1000 C. A greenish yellow pigment having the crystal structure of rutile is obtained.

EXAMPLE 25 5.000 grams of HO; (calculated by a calcining loss from titanium hydroxide) +0500 gram of NiO (calculated from NiCO )+0.775 gram of W0 (calculated from H WO +0.482 gram of MoO +0.200 gram of NaF are Well mixed, calcined for half an hour at 600 C. and, after further pulverising, for half an hour at 800 C. A browny-beige pigment which, according to X-ray examination, has a rutile structure -is obtained.

EXAMPLE 26 5.000 grams of anatase+0.050 gram of Li O (calculated from Li CO )+l.620 grams of 815 0 are mixed, calcined for half an hour at 800 C. and, after pulverismg, for half an hour at 1000 C. A White pigment of the structure of rutile is obtained.

EXAMPLE 27 p v 5.000 grams of anatase+0.050 gram of MgO (calculated from MgCO )+0.401 gram of Sb O are mixed, calcined for half an hour at 800 C. and, after pulverising, for half an hour at 1000 C. A white pigment having a rutile structure is obtained.

EXAMPLE 28 5.000 grams of anatase+0.200 gram of ZnO (calculated from ZnCO )+0.796 gram of Sb O are mixed,

9 calcined for half an hour at 800 C. and, after pulverising, for half an hour at 1000 C. A white pigment having a rutile structure is obtained.

EXAMPLE 30 5.000 grams of anatase 0.500 gram of ZnO (calculated from ZnCO 1.988 grams of Sb O are mixed, calcined for half an hour at 800 C. and, after pulverising, for half an hour at 1000 C. A white pigment having a rutile structure is obtained.

EXAMPLE 31 5.000 grams of ana-tase 0.500 gram of Al O (calculated from active A1 1.588 grams of Sb O are intensively mixed, calcined for half an hour at 800 C. and, after pulverising, for half an hour at 1000 C. A white pigment having a rutile structure is obtained.

EXAMPLE 32 5.000 grams of anatase 0.100 gram of A1 0 (calculated from active A1 0 0.318 gram of Sb O 0.200 gram of NaF are mixed, calcined for half an hour at 800 C. and, after pulverising, for half an hour at 1000 C. A white pigment having a rutile structure is obtained.

EXAMPLE 33 5.000 grams of anatase 0.500 gram of 62 0 0.863 gram of 811 0 are mixed, calcined for half an hour at 800 C. and, after pulverising, for half an hour at 1000 C. A White pigment having a rutile structure is obtained.

EXAMPLE 34 5.000 grams of anatase 0.200 gram of Sb O 0.222 gram of Sh O are mixed, calcined for half an hour at 800 C. and, after pulven'sing, for half an hour at 1000 C. A white pigment having a rutile structure is obtained.

EXAMPLE 35 EXAMPLE 36 5.000 grams of anatase 0.500 gram of Z110 (calculated from ZnCO 1.125 grams of Sb O 0.817 gram of Nb O are mixed, calcined for half an hour at 800 C. and, after pulverising, for half an hour at 1000 C. A white pigment having a rutile structure is obtained.

EXAMPLE 37 5.000 grams of anatase 0.020 gram of Li O (calculated from Li CO 0.325 gram of 811 0 0.444 gram of T21 O are mixed, calcined for half an hour at 800 C. and, after pulverising, for half an hour at 1000 C. A yellowish white pigment having a rutile structure is obtained.

EXAMPLE 38 5.000 grams of anatase 0.020 gram of Ll (calculated from Li CO 0.887 gram of Ta O are mixed, calcined for half an hour at 800 C. and, after pulverising, for half an hour at 1000 C. A yellowish white pigment having a rutile structure is obtained.

EXAMPLE 39 5.000 grams of anatase 0.500 gram of V 0 (calculated from NH VO 0.027 gram of Li O (calculated from Li CO are mixed, calcined for half an hour at 800 C. and, after pulverising, for half an hour at 1000 C. A blackish brown substance which has the structure 10 of rutile, according to X-ray analysis, and which also possesses pigment fineness is obtained.

EXAMPLE 40 5.000 grams of anatase 0.500 gram of V 0 (calculated from NH VO 0.111 gram of MgO (calculated from MgCO are mixed, calcined for half an hour at 800 C. and, after pulverising, for half an hour at 1000 C. A dark violet brown pigment having a rutile structure is obtained.

EXAMPLE 41 5.000 grams of anatase 0.500 gram of ZnO (calculated from NH VO are mixed, calcined for half an hour at 800 C. and, after pulverising, for half an hour at 1000 C. A blackish grey pigment having a rutile structure is obtained.

EXAMPLE 42 5.000 grams of anatase 0.200 gram of MnO (calculated from MnCO 0.513 gram of V 0 (calculated from NH VO are mixed, calcined for half an hour at 800 C. and, after pulverising, for half an hour at 1000 C. A dark brown pigment having a violet cast and the structure of rutile is obtained.

EXAMPLE 43 5.000 grams of anatase 0.200 gram of FeO (calculated from FeCO 0.507 gram of V 0 (calculated from NH VO are mixed, calcined for half an hour at 800 C. and, after pulverising, for half an hour at 1000 C. A dark violet brown pigment having the structure of rutile is obtained.

EXAMPLE 44 5.000 grams of anatase 0.200 gram of C00 (calculated from C000 0.486 gram of V 0 (calculated from NH VO are nu'xed, calcined for half an hour at 800 C. and, after further mixing, for half an hour at 1000 C. A deep dark brown pigment of a greenish cast and having the structure of rutile is obtained.

EXAMPLE 45 5.000 grams of anatase 0.500 gram of NiO (calculated from NiCO 1.218 grams of V 0 (calculated from NH VO are mixed, calcined for half an hour at 800 C. and, after pulverising, for half an hour at 1000 C. A black-grey pigment having a bluish cast and which is of a rutile structure is obtained.

EXAMPLE 46 5.000 grams of anatase+0.l00 gram of NiO (calculated from NiCO )+0.244 gram of V 0 (calculated from NI-I VO )|-0.l00 gram of NaF are mixed, calcined for half an hour at 800 C. and, after pulverising, for half an hour at 1000 C. A reddish yellow brown pigment having the structure of rutile is obtained.

EXAMPLE 47 5.000 grams of anatase+0.200 gram of CuO (calculated from CuCO )+0.457 gram of V 0 (calculated from NH VO are mixed, calcinedfor half an hour at 800 C. and, after pulverising, for half an hour at 1000 C. A grey pigment having a violet cast and the structure of rutile is obtained.

EXAMPLE 48 5.000 grams of anatase+0.500 gram of A1 0 (calculated from active Al O )|-0.893 gram of V 0 (.calculated from NH VO are mixed, calcined for half an hour at 800 C. and, after pulverising, for half an hour at 1000 C. A black-grey pigment having the structure of rutile is obtained.

EXAMPLE 49 5.000 grams of anatase+0.500 gram of Ga O +0.485 gram of V 0 (calculated from NH VO are mixed, calcined for half an hour at 800 C., and, after pulverising, for half an hour at 1000 C. A very dark brown pigment having a rutile structure is obtained.

1 w EXAMPLE 50 5000 grams of anatase+0.800 gram of Sb O +0.500 gram of V (calculated from NH VO are mixed,

calcined for half an hour at 800 C. and, after pulverising, for half an hour at 1000 C. A black-brown pigment of rutile structure is obtained.

EXAMPLE 5 1 5.000 grams of anatase+0.200 gram of Cr O +0.239 gram of V 0 (calculated from NI-I VO are mixed, calcined for half an hour at 800 C. and, after pulverising, for half an hour at 1000 C. A dark earth-brown pigment of rutile structure is obtained.

EXAMPLE 52 5.000 grams of anatase+0.500 gram of MnO (from MnCO as source for Mn O )+0.641 gram of V 0 (calculated from NH VO are mixed, calcined for half an hour at 800 C. and, after pulverising, for half an hour at 1000 C. A dark grey pigment having a violet cast and a rutile structure is obtained.

EXAMPLE 53 5.000 grams of anatase+0.500 gram of Fe O +0.570 gram of V 0 (calculated from NH VO are mixed,

calcined for half an hour at 800 C. and, after pulverising, for half an hour at 1000 C. A dark violet-brown pigment having the crystal structure of rutile is obtained.

EXAMPLE 54 5.000 grams of anatase+0.250 gram of NiO (cal- V culated from NiCO )+0.250 gram of CuO (calculated from CuCO +1.183 grams of V 0 (calculated from NH VO are mixed, calcined for half an hour at 800 C. and, after pulverising, for half an hour at 1000 C. A dark brown greyish pigment having the structure of rutile is obtained.

EXAMPLE 55 5.000 grams of anatase+0.l00 gram of Mn!) (calculated. from MnCO )+0.100 gram of C00 (calculated from CoCO )+0.499 gram of V 0 (calculated from NH VO are mixed, calcined for half an hour at 800 C. and, after pulverising, for half an hour at 1000" C. A dark grey pigment with a violet cast and the structure of rutile is obtained.

7 EXAMPLE 56 5.000 grams of anatase+0.0l1 gram of Li O (calfrom NH VO )+1.755 grams of Bi O (calculated from Bi O are mixed together, calcined for half an hour at 800C. and, after pulverising, for a further half hour at 1000 C. A metallic grey pigment with a rutile structure is obtained. 7

EXAMPLE 60 5.000 grams of anatase+0.500 gram of C00 (calculated from CoCO )+0.304 gram of V 0 (calculated from NH VO )+1.331 grams of Nb O are mixed together, calcined for half an hour at 800 C. and, after pulverising, for half an hour at 1000 C. A deep brown pigment with a rutile structure is obtained.

EXAMPLE 61 5.000 grams of anatase+0.500 gram of NiO (calculated from NiCO )+0.304 gram of V 0 (calculated from NH VO )+2.220 grams of Ta O are mixed, calcined for half an hour at 800 C. and, after pulverising, for half an hour at 1000 C. A yellow-brown pigment of which approximately 10% has an anatase structure and approximately 90% a rutile structure is obtained.

EXAMPLE 62 5.000 grams of anatase+0.500 gram of ZnO (calculated from ZnCO )+0.559 gram of V 0 (calculated from NH VO )+0.442 gram of MoO +0.200 gram of NaF are mixed well, calcined for half an hour at 700 C. and, after pulverising, for half an hour at 800 C. A grey-brown pigment which, according to X-ray analysis, has a rutile structure is obtained.

EXAMPLE 63 from MnCO +0010 gram of C00 (calculated from culated from Li CO )+0.200 gram of Fe O +0.428

gram of V 0 (calculated from NH VO are mixed, calcined for half an hour at 800 C. and, after pulverising, for half an hour at 1000 C. A dark violet-brown pigment with a rutile structure is obtained.

EXAMPLE 57 r 5.000 grams of anatase+0.500 gram ZnO (calculated from ZnCO )+0.5O0 gram of cr,o +1.717 grams of V 0 (calculated from NH VO are mixed, calcined for half an hour at 800 C(and, after pulverising, for half an hour at 1000 C. A black-grey pigment of rutile structure is obtained.

EXAMPLE 5 8 5.000 grams of anatase+0.500 gram of NiO (calculated from NiCO )+0.609 gram of V 0 (calculated from NH VO )+1.080 grams of Sb O 'are mixed well, calcined for half an hour at 800 C. and, after pulverising, for half an hour at 1000 C. A pale reddish-brown pigment with a rutile structure is obtained.

EXAMPLE 59 5.000 grams of anatase+0.500 gram of MnO (calculated from MnCO )+0.642 gram of V 0 (calculated 7 is obtained.

CoCO )+0.010 gram of Fe 0 +0.010 gram of Cr O +0.452 gram of V 0 (calculated from NH VO )+0.456 gram of Sb O +0.065 gram of Bi O (calculated from Bi O +0.0179' gram of U0 (calculated from uranyl nitrate) +0.0175 gram of Nb 0 are mixed, calcined for half an hour at 800 C. and, after pulverising, for half an hour at 1000 C. A dark brown pigment with a grey cast and of the structure of rutile EXAMPLE 65 5.000 grams of anatase+0.500 gram of MnO' (calculated from MnCO )+2,280 grams of 815 0 are mixed, calcined for half an hour at 800 C. and, after pulverising, for half an hour at 1000 C. A medium brown pigment having a red cast and a rutile or trirutile structure is obtained.

EXAMPLE 66 5.000 grams of anatase+0.100 gram of FeO (calculated from FeCO +0.450 gram of 813 0 are mixed, calcined for half an hour at 800 C. and, after pulverising, for half an hour at 1000 C. A grey pigment with a green cast, of which approximately 20% has an anatase structure and approximately a rutile structure, is obtained.

EXAMPLE 67 5.000 grams of anatase+0.500 gram of'FeO (calculated from FeCO )+2.250 grams of Sb O are mixed, calcined for half an hour at 800 C. and, after pulverising, for half an hour at 1000 C. A grey pigment with a green cast and of pure rutile structure is obtained.

13 EXAMPLE 68 5.000 grams of anatase+0.500 gram of C110 (calculated from CuCO )+2.030 grams of Cb are mixed, calcined for half an hour at 800 C. and, after pulverising, for half an hour at 1000 C. A lemon-yellow pigment which has a rutile structure is obtained.

EXAMPLE 69 5.000 grams of anatase+0.200 gram of CuO (calculated from CuCO )+0.8l2 gram of Sb O +0.050 gram of NaF are mixed, calcined for half an hour at 800 C. and, after pulverising, for half an hour at 1000 C. A yellow pale green pigment having a rutile structure is obtained.

EXAMPLE 70 5.000 grams of anatase+0.500 gram of V 0 (as source for V 0 +0.889 gram of Sb O are mixed, calcined for half an hour at 800 C. and, after pulverising for half an hour at 1000 C. A black-brown pigment having a rutile structure is obtained.

EXAMPLE 71 5.000 grams of anatase+0.100 gram of Cr O +0.213 gram of Sb O are mixed, calcined for half an hour at 800 C. and, after pulverising, for half an hour at 1000 C. A yellow-olive pigment with the structure of rutile is obtained.

EXAMPLE 72 obtained.

EXAMPLE 74 5.000 grams of anatase+0.200 gram of Fe O +OA05 gram of Sb 'O are mixed, calcined for half an hour at 800 C. and, after pulverising, for half an hour at 1000 C. A grey-olive pigment, of which approximately 30% has an anatase structure and approximately 70% a rutile structure, is obtained.

EXAMPLE 75 5.000 grams of anatase+0.200 gram of Fe O +O.405 gram of Sb O +0.200 gram of NaF are mixed, calcined for half an hour at 800 C. and, after pulverising, for half an hour at 1000 C. A greenish yellow pigment having a rutile structure is obtained.

EXAMPLE 76 5.000 grams of anatase+0.250 gram of Cr O -i-0250 gram of CuO (calculated from CuCO )+1.550 grams of Sb O are mixed, calcined for half an hour at 800 C. and, after pulverising, for half an hour at 1000 C. A beige-coloured pigment having a rutile structure is obtained.

EXAMPLE 77 5.000 grams of anatase+0.250 gram of Fe O +0.25O gram of MnO (calculated from MnCO )+1.645 grams of Sb O are mixed, calcined for half an hour at 800 C. and, after pulverising, for half an hour at 1000 C. A reddish-brown pigment having a rutile structure is obtained.

EXAMPLE 78 5.000 grams of anatase+0.200 gram of Fe O +0.156 gram of Bi O (from nitrate) +0303 gram of Sb 0 are mixed, calcined for half an hour at 800 C. and,

1 4 after pulverising, for half an hour at 1000 C. A yellowbeige pigment having a rutile structure is obtained.

EXAMPLE 79 5.000 grams of anatase+0.500 gram of CuO (calculated from CuCO )+1.015 grams of Sb O +0.835 gram of N'o O are mixed, calcined for half an hour at 800 C. and, after pulverising, for half an hour at 1000 C. A light greenish yellow pigment having a rutile structure is obtained.

EXAMPLE 80 5.000 grams of anatase+0.500 gram of Cr O +0.268 gram of Sb O +1.091 grams of Ta O are'mixed, calcined for half an hour at 800 C. and, after pulverising for half an hour at 1000. A greyish-olive pigment having a rutile structure is obtained.

EXAMPLE 81 Titanium hydroxide sludge (TiO solid content 5.000 grams) is mixed with 0.500 gram of CuO (calculated from CuCO )+0.508 gram of Sb 0 +0.678 gram of M00 and is calcined for half an hour at 700 C. and, after pulverising for a further half hour at 800 C. An olive-green pigment having a rutile structure is obtained.

EXAMPLE 82 5.000 grams of TiO +0.500 gram of MnO (calculated from MnCO )+l.140 grams of Sb O +1.010 grams of U0 (from uranyl nitrate) are mixed, calcined for half an hour at 800 C. and, after pulverising, for half an hour at 1000 C. A red-brown pigment of mixed rutile and trirutile structure is obtained.

EXAMPLE 83 5.000 grams of anatase+0.100 gram of MgO (calculated from MgCO )+0.l00 gram of Mn() (from MnCO )+0.010 gram of Fe O +0.010 gram of Cr O are mixed with 0.452 gram of V 0 (from NH VO 0.456 gram of Sb O +0.0654 gram of Bi O (from nitrate) +0.0179 gram of U0 (from nitrate) +0.0175 gram of Nb O and the mixture is calcined for half an hour at 800 C. and, after pulverising, for a further half hour at 1000 C. A dark brown pigment having a rutile structure is obtained.

EXAMPLE 84 5.000 grams of anatase+0.500 gram of C00 (calculated from CoCO )+l.774 grams of Nb O are mixed, calcined for half an hour at 800 C. and, after pulverising, for half an hour at 1000 C. A brownish-beige pigment having arutile structure is obtained.

EXAMPLE 85 5.000 grams of anatase+0.500 gram of NiO (calculated from NiCO )+2.960 grams of Ta O +0.25O gram of NaF are mixed, calcined for half an hour at 800 C. and, after pulverising, for half an hour at 1000 C. A lemon-yellow pigment of predominantly rutile lattice, which is partly disturbed, is obtained.

EXAMPLE 86 5.000 grams of Ti0 (calculated from hydrate sludge) are mixed with 0.500 gram of NiO (calculated from NiCO )|0.890 gram of Nb O +L480 grams of Ta O and calcined first for half an hour at 800 C. and then, after pulverising and the addition of 0.250 gram of NaF, for half an hour at 1000 C. A lemon-yellow pigment of predominantly rutile structure is obtained.

EXAMPLE 87 5.000 grams of anatase+0.500 gram of MO (calculated from NiCO )+0.500 gram of C00 (calculated from CoCO )+1.774 grams of Nb O +2.960 grams of Ta O are mixed, calcined for half an hour at 800 C., then after pulverising, for half an hour at 1000 C. and finally,

after further pulverising, for 2 hours at 1100 C. An

orange-brown pigment of rutile structure is obtained.

EXAMPLE 88 5.000 grams of TiO (calculated from hydrate sludge) +0500 gram of C (calculated from CoCO ).|-0.960 gram or" M00 are mixed, calcined for half an hour at 700 C. and, after pulverising, for half an hour at 800 C. A brown-grey pigment of quite predominantly anatase structure is obtained.

EXAMPLE 89 5000 grams of H0 (calculated from hydrate sludge) +0.500 gram of C00 (calculated from CoCO )-}0.960 gram of M00 are mixed, calcined for half an hour at 700 C. and, after pulverising and the addition of 0.200 gram of NaF, for a further half hour at 800 C. A dark brown pigment of rutile structure is obtained.

EXAMPLE 90 5.000 grams of anatase+0.200 gram of C00 (calculated from CoCO )-l0.764 gram of U0 (calculated from uranyl nitrate) are mixed, calcined for half an hour at 800 C. and, after pulverising, for half an hour at 1000 C. A yellow-brown pigment of rutile structure is obtained.

' EXAMPLE 91 5.000'grazns of anatase'-|-0.200 gram of NiO (calculated from NiCO )+0.385 'gram of M00 are mixed, calcined for half anhour at 600 C. and, after pulverising, for half an hour at 800 C. A brown-orange pigment of anatase structure is obtained.

EXAMPLE 92 5.000 grams of anatase+0.200 gram of NiO (calculated from NiCO )+0.776 gram of U0 (from nitrate) are mixed, calcined for half an hour at 800 C., and, after pulverising, for half an hour at 1000 C. An oliveyellow pigment of rutile structure is obtained.

7 EXAMPLE 93 7 5.000 grams of TiO (calculated from hydrate sludge) +0500 gram of C00 (calculated from CoCO )+0.737

NaF are mixed, calcined for half an hour at 700 C. and,

after pulyerising, for half .an hour at 800 C. A dark brown pigment with a violet cast and which is of rutile structure is obtained.

EXAMPLE 94 5.000 grams of anatase+0.500 gram of NiO (calculated from NiCO )+0.890 gram of Nb O +0.958 gram of U0 (from nitrate) are mixed, calcined for half an hour at 800 C. and, after pulverising, for half an hour at 1000 C. A brownish yellow-olive pigment of rutile structure is obtained.

EXAMPLE 95 EXAMPLE 96 7 5.000 grams of anatase+0.l00 gram of Li O (calcugram of Ta O +0.720 gram of MoO +0.200'gram of V V 16 MoO +0.734 gram of U0 (from nitrate) are mixed, calcined for half an hour at 800 C. and, after pulverising, for half an hour at...100 C. A dark red-brown pigment of clearly rutile structure is obtained.

EXAMPLE 97 EXAMPLE 98 5.000 grams of TiO (calculated from hydrate sludge) +0500 gram of Ni() (calculated from NiCO )-l-l.080 grams of Sb O +0.482 gram of MoO +0.100 gram of NaF are mixed, calcined for half an hour at 700 C. and, after pulverising, for half an hour at 800 C. A light brown-yellow pigment of which approximately 40% has an anatase structure and approximately 60% a rutile structure is obtained.

7 EXAMPLE 99 5.000 grams of anatase+0.500 gram of NiO (calculated from NiCO )+1.080 grams of Sb O +L665 grams of Bi O (calculated from bismuth nitrate) are mixed, calcined for half an hour at 800 C. and, after pulverising, for half an hour at 1000 C. A light yellow pigment with a brownish cast and with a predominantly rutile and trimtile structure is obtained.

EXAMPLE 100 EXAMPLE 101 5.000 grams of anatase+0.250 gram of C00 (calculated from CoCO are mixed with the quantities of oxidic compounds and with the quantities of Sb O indicated in Table 1 and the mixtures are then calcined for half an hour at 800 C. and after pulverising, for half an hour at 1000 C. The coloured pigments listed with rutile or trirutile structures as listed are obtained.

Table 1 lated from Li CO )+0.100 gram of ZnO (calculated from ZnCO )+0.100 gram of C00 (from CoCO )+0.l00 gram of NiO (from NiCO )|-0.100 gram ,of FeO' (from FeCO3)+0.l00 gram of MnO (from MnCO )+0:100 gram of Al O +0.100 gram of Cr O +0.100 gram of SnO +0.l00 gram of CuO (from CuCO +0.711' gram of Nb O +1.761 grams of Ta O +L446 grams of OF CoQ, COLOUR, AND X-RAY ANALYSIS y N o 2: grams of lowgrams Colour X-ray valence oxide of structure SbgOs a 0.10 g. of Li2O- 4. 328 Brownish light Rutile strucorange-yellow. ure. b 0.25 g. of MgO 3. Light-orange Rutiletriyellow. rutile. c-- 0.25 g. of ZnO 2.073 Brownish yellow- Rutile-triorange. rutile. d 0.25 g. of MnO 2. 221 Yellowish brown.- Do. 9..." 0.25 g. of FeO 2. 206 Pale brown- 7 Do.

yellow. 1..." 0.25 g. of A1203--.. 1. 873 Yellow-orange Rutlle. g 0.25 g. of Ga20a--.- 1. 511 Brownish yellow- Do. orange. h- 0.25 g. of OrzO3. 1. 615 do Do. i 0.25 g. of Fe2O3 1. 585 Dirty yellow- Do.

. orange.

EXAMPLE 102 5.000 grams of anatase+0.250 gram of NiO (calculated from NiCO are mixed with the quantities of oxidic compounds and with the quantities of Sb 0 indicated in Table 2 and the mixture then calcined for half an hour at 800 C. and, after pulverising, for half. an. hour at 1000 C. in each case a pigment with arutile or trirutile structure as listed in the table is obtained.

17 Table 2 1! No 2 grams of lowgrams Colour X-ray valence oxide of structure a. 0.10 g. 01' L120... 4.328 Greenish-yellow-.- Rutile. b 0.25 g. of, MgO 3. 130 Greenish white- Rutile-trlgrey. rutile badly crystallised. c"--- 0.25 g. of ZnO 2. 073 Light lemon- Rutile.

' yellow. d 0.25 g. of MnO 2. 221 Medium brown... Do. e 0.25 g. of FeO 2. 200 Light olive-grey. D0. f 0.50 g. of 0110 4.190 Yellow-green Do. g 0.25 g. of Al2O3 1. 873 W hite-green- Rutile triyellow. rutile. 12..-- 0.25 g. of GazO3 1. 511 Green-yellow Rutile. i-.." 0.25 g. of Crqognh 1. 615 Browm'sh-yellow.. Do. k 0.25 g. of 102203.--. 1. 585 Light 'olivegrey. Do.

Here combined with 0.50 g. of NiO.

EXAMPLE 5.000 grams of anatase+0.500 gram of Ni+1.082 grams of Sb O +0.890 gram of Nb O +1.000 gram of Zr0 (calculated from nitrate) are mixed, calcined for half an hour at 800 C., and, after pulverising, for half an hour at 1000 C. A lemon-yellow pigment of predominantly rutile structure is obtained.

EXAMPLE 104 5.000 grams of anatase+0.100 gram of MgO (calculated from MgCO )+0.100 gram of MnO (calculated from MnCO )+0.l00 gram of C00 (calculated from CoCO )i-0.2 00 gram of NiO (calculated from NiCO +0100 gram of Fe O +0.100 gram of Cr O +0.01O gram of (321 0 are mixed with 2.108 grams of Sb O 0.389 gram of Nb O +0589 gram of Ta O and the mixture is then calcined for half an hour at 800 C. and, after pulverising, for a further half hour at 1000 C. A light yellow-brown pigment having a rutile structure is obtained.

EXAMPLE 105 ture is obtained.

' EXAMPLE 107 5.000 grams of TiO (hydrate sludge)+0.200 gram of CuO (calculated from CuCO )+0.577 gram of AS205 (calculated from HgASOQ are mixed, calcined for half an hour at 700 C., and, after pulverising, for half an hourat 800 C. A white-grey pigment having an anatase structure is obtained.

EXAMPLE 108 5.000 grams of TiO (hydrate sludge)+1.000 gram of CuO (calculated from CuCO )+0.500 gram of ZnO (calculated from ZnCO )+0.430 gram of AS205 (calculated from H AsO )+2.426 grams of M00 are mixed, calcined for half an hour at 700 C., and, after pulverising, for half an hour at 800 C. A green grey sandy pigment of quite predominantly rutile structure is obtained.

EXAMPLE 109 5.000 grams anatase and 0.200 gram of ZnF are mixed, calcined for half an hour at 800 C. and for half an hour 18 at 1000 C. A yellowish white pigment with the crystal structure of rutile is obtained.

EXAMPLE 5.000 grams of anatase are mixed with 0.500 gram of MnF' calcined for half an hour at 800 C. and for half an hour at 1000 C. A dark violet-brown pigment with a rutile structure is obtained.

EXAMPLE 11 1 5.000 grams of anatase are mixed with 0.500 gram of COF2, calcined for half an hour at 800 (Land, after being pulverised, for half an hour at 1000 C; A reddish-brown pigment which is shown by X-ray analysis to have a rutile structure is obtained.

EXAMPLE 112 5000 grams of anatase and 0.500 gram of NiF are mixed, calcined for half an hour at 800 C. and, after beingpulverised, for half an hour at 1000 C. A bright lemon yellow pigment of rutile structure is obtained.

' EXAMPLE 113 5.000 grams or" anatase, 0.500 gram of CrF (calculated from CrF 3H O) and 0.119 gram of LiF are mixed to: gether, calcined for half an hour at 800 C and, after pulverisation, for half an hour at 1000 C. A dark brown pigment of rutile structure is obtained;

EXAMPLE 115 5.000 grams of anatase, 0.200 gram of FeF (calculatedfrom FeF .3H O) and 0.018 gram of Li O (calculated from Li CO are mixed together, calcined for half an hour at 800 C., and, after further pulverisation, fiorha'lf an hour at 1000 C. A light beige pigment of rutile structure is obtained.

EXAMPLE 116 5.000 grams of anatase, 0.050 gram of A11 (calculated from AlF JI-I O) 0.500 gram of C1'F3 (calculated from CrF .3H O), 0.500 gram of FeF (calculated from FeF .3H O) and 0.148 gram of L (calculated from' Li CO are mixed together, calcined for half an hour at 800 C. and, after pulverisation, for half an hour at 1000? C. A dark brown pigment with a reddish tinge andhaving a rutile structure is obtained.

EXAMPLE 117 5.000 grams of anatase, 0.500 gram of AlF (calculated from AlF .3H O) and 0.484 gram of ZnO (calculated from ZnCO are mixed, calcined for half an hour at 8001 C. and, after pulverisation; for half an hdur'at 1000f C. A yellowish white pigment of rutile struetu'reis obtained.

EXAMRLE l 18 5.000 grams of anatase, 0.500 gram of AlF (calculated from A1Fg3H O) and 0.422 gram of MnO (calculated from MnCO are m xed, calcined for half an hourat 800 C., and for a further half an hour at 1000 C., after pulverisation. A dark violet-brown pigment of rutile structure is obtained.

EXAMPLE 119 5.000 grams of anatase, 0.500 gram of AlF (calculated from AlF3-3H20) and 0.445 grani of NiO (calculated from NiCO are mixed, calcined for half an hour at 800 C., and for another half an hour at 1000 C. after pulverisation. A pastel-coloured lime-green pigment which has the crystal structure of rutile is obtained.

EXAMPLE 120 5.000 grams of anatase, 0.500 gram of CrF (calculated from CrF .3H 'O) and 0.329 gram of FeO (calculated from FeCO are mixed together, calcined for half an hour at 800 C. and then for another half hour at 1000 C. after pulverisation. A, dark olive brown pigment of rutile structure is obtained;

EXAMPLE 121 5.000 grams of anatase, 0.500 gram of FeF (calculated from FeF .3H O) and 0.314 gram of M110 (calculated from'MnCO are mixed togethenheated for half an hour at 800 C. and, after being further pulverised,

.for half an hour at 1000 C. A dark brown pigment with a violet tinge and having a rutile structure is obtained.

EXAMPLE 122 5.000 grams of anatase, 0.100 gram of ME, (calculated from AlF .3H O) and 0.089 gram of NiO (calculated from NiCo are mixed together, calcined for half an hour at 800 C., pulverised, and then calcined for another half hour at 1000 C. A yellowish-grey pigment substantially 85% of which has a rutile structure and substantially 15% an 'anatase structure, was obtained.

EXAMPLE 123 5.000 grams of anatase, 0.500 gram ctr, (calculated from. CrF .3H O) and 0.697 gram Cr O ar emixed together, calcined for half an hour at 800 C., pulverised,

and then calcined for another half hour at 1000 C. A. dark olive-coloured pigment of rutile structure is obtained.

EXAMPLE 124 5.000 grams of anatase, 0.500 gram of Sb O and 0.040 gram of LiF are mixed together, calcined for half an hour at 800 C., and then for another half hour at 0.029 gram of LiF are mixed together, calcined for half an hour at 800 C., and for another half hour at 1000 C. after pulverisation. A whitish-yellow 'pigment of rutile structure is obtained.

EXAMPLE 128' 5.000 grams of TiO (calculated from titanium hydroxide), 0.500 gram of M00 and 0.090 gram of LiF are mixed together, calcined for half an hour at 600 C.

5.000 grams of rutile, 0.500 gram of W0 (calculated from H WO and 0.056 gram of LiF are mixed together, calcined for half an hour at 800 C. and for another half an hour at 1000 C. after being pulverised. A yellowishwhitish grey pigment of rutile structure is obtained.

EXAMPLE 13 l A mixture of 5.000 grams of anatase and the components indicated in the accompanying table by x g. X +Y g. Y+z g. Z is calcined for half an hour at 800 C. and for another half an hour at 1000" C., after being I pulverised. Pigments which have the colour and the crystal structure set out in the table are obtained. It is to be seen from the table that the systems mentioned in the earlier examples also form solid solutions with one another while maintaining the rutile structure.

Table.Exdmples for N0. 131

No. I g. X y g. Y 2 g. Z Colour of pigments Crystal 7 structure a 0.200 g. 0.200 g. NiFa. Olive brown Rutile. b 0.200 g. do Greenish brown Do. 0.--- 0.200 g. Canary yellow Do. d 0.200 g. Bright yellow green Do. e.'- 0.200 g. Rich dark reddish brown. Do. I"... 0.200 g. Greeru'sh yellow Do. g 0.200 g. Reddish brown Do. 11;--. 0.200 g. Light green D0. in--- 0.200 g. Rich dark reddish brown D0. 11.... 0.045 g. Khaki Do. l 0.038 g. Do. in... 0.034 g. Do. 11---- 0.040 1;. Do. 0--.. 0.033 g. Do. 11.... 0.200 g. Do. q 0.200 g. D0. r 0.200 g. 0.200 g. AlFa Do.

1000 C. after pulverisation. A yellowish-white pigment of rutile structure is obtained.

EXAMPLE 12s 5.000'grams of anatase, 0.2000 gram V 0 (calculated from NH VO and 0.029 gram of LiF are mixed together, calcined for half an hour at 800 C., pulverised, and then calcined for another half hour at 1000 C. A dark-brown pigment of rutile structure is obtained.

EXAMPLE 126 EXAMPLE 127 7 5.000 grams of anatase, 0.500 gram of Ta O and EXAMPLE .132 5.00 grams of SnOg, 0.020 gram of Li O(Li CO and 0.650 gram of Sb O are mixed together, calcined for half an hour at 800 C. for another half an hour at 1000 C. after pulverisation and finally for another half an hour at 1150 C. after further pulverisation. A lightblue pigment of rutile structure is obtained.

EXAMPLE 133 5.00 grams of 'SnO 0.100 gram of MgO(MgCO and 0.802 gram of Sb O are mixed togetherjthe mixture is calcined for half an hour at 1000 C., for half an hour at 1150 C. after pulverisation and for another half an hour at 1350 C. after further pulverisation. A greyishblue pigment with a greenish. tinge and a rutile structure. is obtained.

EXAMPLE 134 5.000 grams of smo 0.200 gram of znoanco and 0.759 gram of Sb O are mixed together, calcined for half an hour at 1000" C., and for another half an hour at 1150 C. after pulverisation. A whitish-blue pigment Wlth a greenish tinge and a rutile structure is obtained.

EXAMPLE 135 5.000 grams of SnO 0.200 gram of MnO(MnCO and 0.912'gram of 813 are mixed together; the mixture calcined for half an hour at 800-. C., pulverised, further calcined for half an hour at 1000 C., and then again pulverised and further calcined for half an hour at 1150 C. A light greyish-brown pigment with a rutile structure is obtained.

EXAMPLE 13 6 5.000 grams of SnO 0.200 gram of 'FeO(FeCO and 0.900 gram of Sb O are mixed together; the mixture is calcined for half an hour at 80 C., for another half an hour at 1000 C. after pulverisation and then, after being pulverised again for a further half hour at 1150 C. A light grey pigment with a rutile structure is obtained. 1

EXAMPLE 13 7 5.000 grams of S110 0.200 gram of CoO(CoCO and 0.864 gram of Sb O are mixed together; the mixture is calcined for half an hour at 800 C., pulverised, calcined for a further half an hour at 1000 C., and again pulverised, and finally calcined for another half an hour at 1150" C. A yellowish-grey pigment with a brown tinge and a rutile structure is obtained.

EXAMPLE 13 5.000 grams of SnO 0.200 gram of NiO(NiCO and 0.866 gram of Sb O are mixed together; the mixture is calcined for half an hour at 800 C., pulverised, calcined for a further half an hour at 1000 C., again pulverised, calcined for another half an hour at 1150 C. and, after being pulverised again, calcined for another half hour at 150 C. An olive-green pigment with a futile structure is obtained, both at 1000 C. and at 1350 C. 4 H

EXAMPLE 139 5.000 grams of SnO 0.500 gram of CuO(CuCO and 2.033 grarnsof Sb O are mixed together; the mixture is heated for half an hour at 800 C., pulverised, and heated again for half an hour at 1000 C., and then pulverised and heated for another half an hour at 1150 C. A brownish-olive coloured pigment with a rutile structure is obtained.

EXAMPLE 140 5.000 grams of SnO 0.200 gram of A1 0 (from Al(OH) and 0.634 gram of Sb O are mixed together;

the mixture is heated for half an hour at 800 C., pulverised, heated for half an hour at 1000 C., pulverised again, heated for half an hour at 1150 C., pulverised yet again, and heated for one hour at 1350 C. A light doveblue coloured pigment with a rutile structure is obtained.

EXAMPLE 141 5.000 grams of SnO 0.500 gram of Ga Og and 0.863 gram of Sb O are mixed together;-the mixture is heated for half an hour at 800 C., pulverised, heated for half an hour at 1000 C., again pulverised, and heated for half an hour at 1150 C., and finally'pulverised yet again and then heated for half an hour at 1350 C. A light grayish-blue pigment with a rutile :structure is obtained.

7 EXAMPLE 142 5.000 grams of 5:10 0.500 gram of Cr O and 1.065 grams of Sb O are mixed together; the mixture is heated for half an hour at 800 C., pulverised, heated for half an hour at 1000 C., pulverisedagaimheated for half an hour at 1150 C., and finally pulverised yet again and then heated for 1 hour'at 1350? C. A yellowish-brown pigment with a rutile structure is obtained.

EXAMPLE 143 5.000 grams of'SnO 0.50 gram of Mn O (MnCO and 1.025 grams of Sb O are mixed together, heated for half an hourat 800 C., pulverised, heated for half an hour at 1000 C., pulverised again and then heated for half an hour at 1150 C. A 'greyish-brown pigment of predominantly rutile structure is obtained.

EXAMPLE 144 5.000 grams of SnO 0.500 gram of Fe O and 1.013 grams of Sb O are mixed together; the mixture is heated for half an hour at 800 C., pulverised, heated for half an hour at 1000 C., pulverised again, heated for a further half hour at 1150 C., and finally pulverised once more and heated for one hour at 1350 C. A light greyish yellow pigment with a rutile structure is obtained.

EXAMPLE 145 5.000 grams of S110 0.050 gram of Li O(Li CO and 0.913 gram of V 0 are mixed together; the mixture is heated for half an hour at 1000 C., pulverised, and

then heated for half an hour at 1150 C. A blackishreddish brown pigment with a rutile structure is obtained.

EXAMPLE 146 5.000 grams of 8e0 0.200 gram of Mg0(MgCO and 0.903 gram of V 0 are mixed together, heated for half an hour at 1000" C., pulverised, and then heated for half an hour at 1150" C. An olive-brown pigment with a rutile structure is obtained.

EXAMPLE 147 5.000 grams of S110 0.500 gram of ZnO (ZnCO and 1.118 grams of V 0 are mixed together; the mixture is heated for half an hour at 1000" C., pulverised, and heated for a further half hour at 1150 C. An olivecoloured pigment with a yellowish tinge is obtained, the pigment having a rutile structuref EXAMPLE 148 5.000 grams of SnO 0.500 gram of A1 0 (Al(OH) and 0.892 gram of V 0 are mixed together; the mixture is' heated for half an hour at 1000? C., pulverised, heated for a further half hour at 1000 C., and, after being pulverised again, is heated for another half an hour at 1150 C. A brownish-yellow olive pigment with a rutile structure is obtained.

EXAMPLE 149 5.000 grams of 5110;, 0.500 gram of Al O (Al(OH) and 1.304 grams of Nb O are mixed together; the mixture is heated for half an hour at 1000 C, pulverised, heated for half an hour at 1150 C., and, after further pulverisation, heated for one hour at 1350 C. A white pigment with a rutiie structure is obtained, both at 1150 C. and at 1350 C.

EXAMPLE 150 0.654 gram of W05 and 0.200 gram of MaF are mixed together, heated for half an hour at 1000 C. and, after pulverisation for half an hour at 150C. A light grey pigment with a rutile structure is obtained.

EXAMPLE 152 5.000 grams of S110 0.200 gram of FeO.(F eCO and 0.646 gram of W are mixed together; the mixture is heated for half an hour at 1000 C., pulverised, heated for half an hour at 1150 C. and finally pulverised again and then heated for one hour at 1350 C. A greyish pigment with a brownish tinge and a rutile structure is obtained both at 1150 C. and at 1350 C.

EXAMPLE 1 3 5.000 grams of SnO 0.200 gram of Co() (c000 0.618 gram of W0 and 0.200 gram of NaF are mixed together, heated for half an hour at 1000 C., pulverised, and then heated for another'half hour at 1150 C. A greyish blue pigment with a greenish tinge and a rutile structure is obtained.

EXAMPLE 154 5.000 grams of SE8 0.200 gram of NiO ('NiCOQ and 0.620gr-am of W0 are mixed together, heated for half an hour at 1000 C., pulverised, heated for half an hour at 1150 C., and then pulverised again and heated for 1 hour at 1350 C. A yellowish-grey pigment with a rutile structure is obtained, both at 1150 C. and at 1350" C.

EXAMPLE 155 5.000 grams of SnO 0.500 gram of Cr O and 0.763 gram of W0 are mixed together; the mixture is heated for half'an hour at 1000 C., pulverised, heated for half r A 24 after being pulverised, for another half hour at 1000 C. A greyish-brown pigment of rutile structure is obtained.

EXAMPLE 162 5.000 grams of smo and 2.000 grams'ofNiF are mixedtogether, heated for half an houi at 1000 C. and, after being pulverised, for another half an hour at 1150 C. A greyish-yellow pigment of a rutile structure or rutile over structure is obtained. i

EXAMPLE 163 i 5.000 grams of Sn0 and, 2.000 grams of CuF are mixed together, heated for half an hour at 1000 C. and,

an hour at 1150 C. and finally pulverised and heated again, for one hour at 1350" C. A grey pigment with a rutile structure is obtained, both at 1150 C. and at 1350 C.

EXAMPLE 156 5.000 grams of SnO 0.500 gram of R203 and 0.726

gram' of W0 are mixed together, heated for half an hour at 1000 C., pulverised, heated for half an hour at 1150" C., and finally pulverised again and re-heated for one hour at 135 0 C. A dark grey pigment with a rutile structure is obtained, both at 1150 C. and at 1350" C.

EXAMPLE 157 gram of V 0 are mixed together; the mixture is heated for half an hour at 1000 C., pulverised, and then heated for half an hour at 1150 C. A reddish dark brown pigment with a rutile structure is obtained.

EXAMPLE 159 7 5.000 grams or" S110 and 1.000 gram of ZnF are mixed together; the mixture is heated for half an hour at 800 C., pulverised, and then heated for half an hourat 1000 C. A whitish-grey pigment with a disturbed rutile structure is obtained.

' EXAMPLE 160 5.000 grams of SnO and 1.000 gram of CoF are mixed together, heated for half an hour at 1000 C., and after being pulverised, for another half hour at 1150, C. A dark greenish-blue pigment of somewhat disturbed rutile structure is obtained.

EXAMPLE 161 5.000 grams of SnO and 1.000 gram of MnF are mixed together, heated for half an hour at 800 C. and,

after being pulverised, for half an hour at 1150 C. in air. A greyish-brown pigment with a violet tinge and a rutile structure is obtained.

EXAMPLE 164 5.000 grams of SnO 0.476 gram of LiF and 2.000 grams of CrF are mixed, heated for half an hour at 1000 C., pulverised,:and heated foranother half hour at 1150 C. A violet-red pigment of a rutile structure or rutile over structure is obtained.

' EXAMPLE 165 5.000 grams of S110 0.460 gram of LiF- -and 2.000 grains of FeF are mixed; the mixture is heated for half an hour at 1000 C. and, after pulverisation, for half an hour at 1150 C. A medium grey pigment with a rutile structure is obtained. A 7

EXAMPLE 166 5.000 grams of SnO 0.1765 gram of Li O (from Li CO and 2.000 grams of FeF are mixed together, heated for half an hour at 1000 C., pulverised, and then heated for another half hour at 1150 C. A grey pigment with da slight greenish tinge and a rutile structure is obtaine EXAMPLE 167 5.000 grams of S110 0.0913 gram of Li O (from Li CO and 1.000 gram of CrF are mixed, heated for half an hour at 1000 C., pulverised, and then heated for half an hour at 1150 C. A violet-red pigment which has a rutile structure is obtained.

EXAMPLE 168 1 5.000 grams of SnO 2.000 grams of FeF and 1.410 grams of CuO (from CuC0 are mixed; the mixture is heated for half an hour at 1000 C., and heated again, after pulverisation, for half an hour at 1150 C. A blacklsh-grey pigment with a rutile structure is obtained.

EXAMPLE 169 5.000 grams of SnO 0.224 gram of LiF and 2.000 grams of W0 are mixed together; the mixture is heated for half an hour at 1000 C. and, after pulverising, for half an hour at 1150 C. A greyish-blue pigment with a greenish tinge and a rutile structure is obtained.

EXAMPLE 170 5.000 grams of SnO 0.0907 gram of LiF and 1.000 gram of U0 (from ,uranyl nitrate) are mixed together and heated for half an hour at 1000 C. and, after pulverisation forhalf anhour at 1150 C. A greyishbeige pigment with a rutile structure is obtained.

EXAMPLE 171 5.000 grams of SnO 0.411 gram of Cu O and 2.000

' grams of W0 are mixed together and heated in a stream of pure nitrogen for half an hour at 800 C., pulverised,

25 and then heated for another half hour at 1000 C. A dark grey pigment with a rutile structure is obtained.

EXAMPLE 172 5.000 grams of SnO 0.359 gram of Cu O and 2.000 grams of Nb O are mixed and heated in a stream of pure nitrogen for half an hour at 800 C., pulverised, and then heated for half an hour at 1000 C. A rich brownishorange pigment with a rutile structure is obtained.

EXAMPLE 173 5.000 grams of SnO 0.500 gram of ZnO (from ZnCO and 1.412 grams of A5 are mixed, heated for half an hour at 900 C., pulverised, and then heated for half an hour at 1000 C. A yellowish white pigment with a rutile structure is obtained.

EXAMPLE 174 5.000 grams of smo 0.500 gram of NiO (from NiCO and 1.5375 grams of AS205 are mixed together, heated for half an hour at 900 C., pulverised, and then heated for one hour at 1000 C. A light greenish yellow pigmerit of somewhat disturbed rutile structure is obtained.

' EXAMPLE 175 5.000 grams of SnO 0.500 gram of C00 (from COCO3) and 1.533 grams of AS205 are mixed together, heated for half an hour at 900 C., pulverised and then heated for another half hour at 1000 C. A violet pigment with a rutile structure is obtained.

EXAMPLE 1 7 6 5.000 grams of smo 0.500 gram of CuO (from CuCO and 1.444 grams of As O are mixed together, heated for half an hour at 900 C., pulverised, and then heated for another half hour at 1000 C. A bluish-green pigment with a rutile structure is obtained.

EXAMPLE 178 5.000 grams of 'SnO 1.000 gram of P6 0, and 1.439 grams of AS205 are mixed together, heated for half an hour at 900 C., pulverised, and then heated for another half hour at 1000 C. A blackish-grey pigment with a rutile structure is obtained.

EXAMPLE 179 5.000 grams of SnO 0.500 gram of Cr O and 0.756 gram of A5 0 are mixed together, heated for half an hour at 900 C., pulverised, and then heated for another half hour at 1000 C. A greenish-grey pigment with a rutile structure is obtained.

EXAMPLE 180 0.050 gram of Li O (calculated from Li CO and 1.624 grams of Sb O are mixed together, heated for half an hour at 800 C., pulverised, and then heated for half an hour at 1000 C. A greenish-white pigment with a rutile or tn'rutile structure, LiSb O is obtained.

EXAMPLE 181 0.500 gram of V 0 (calculated from NH VO and 0.889 gram of Sb O are mixed together, heated for half an hour at 800 C., pulverised, and then heated for half an hour at 1000 C. A blackish-grey substance with a trlrutile structure, VSbO is obtained.

EXAMPLE 182 1.000 gram of A1 0 (calculated irorn Al(OH) 26 Merck) and 3.174 grams of Sb 0 are mixed-see the table belowwith x g. X +y g. Sb O heated for half an hour at 800 C., pulverised, and then heated for half an hour at 1000 C. Coloured pigments with a trirutile structure as described in the table are obtained.

N0. 1g. X yg. 001011: Added X-ray S0205 compound structure b 0.50 g. MgO. 4.010 Gregugsh MgsbzOan Trlrutile.

w 1 e. c.. 0.50 g. Zn0. 1.987 do ZnSbz0a Do.

0.50 g. FeO 2.252 Light grey FOSbaOe-. Trlrutlle diswith yellow turbed. Binge (1,100 9.--- 0.50 g. 000. 2.100 Light; beige 008020 Triruttle.

with greyish tinge. 1..-- 0.50 g. NiO. 2.160 Liglhfofieg) NlSbz00 Do. g 0.50 g. CuO- 2. 030 Whitishgrtiein 011313205... 'rr uugug dislll e h 0.50 g. V10 0.880 Reddish VsbO Triruttle or brown. rutile disturbed. k 0.50 g. OM03. 1.070 Greyish green CrSbO4 D0.

EXAMPLE 183 0.500 gram of Ga O and 0.863 gram of Sb O are mixed with x g. X+y g. Sb O heated for half an hour at 800 C., pulverised, and then heated for half an hour at 1000 C. Coloured pigments with a trirutile structure as indicated in the following table are obtained.

N0. 1 g. X .1/ g. Colour Added X-ray SbgO compound structure a 0.05 g. LizO 1. 624 Whitish grey LiSbgOg.-- Trlrutlle. b 0.50 g. MgO- 4. 010 Very light MgSbgO L D0.

c.- 0.50 g. ZnO 1. 987 Bluish-tinged ZnSb20u Do.

light grey.

d-- 0.50 g. FeO 2.252 Light greyish FeSbzO0- Trirutile brown. poor.

e 0.50 g. 000.- 2. 160 Beige 005 0206" Trirutlle.

f. 0.50 g. NiO 2. Greyish- NiSbaOu. Trlrutile or tinged green rutile. (1,100 0.).

g.- 0.50 g. CuO- 2.030 Light lime CuSbzOrn- Trirutlle.

green.

h 0.50 g. V2O5 0. 889 Olive brown VSbO Do.

EXAMPLE 184 0.500 gram of V 0 and 0.889 gram of Sb O are mixed with x g. X +y g. sb o see the table belowheated for half an hour at 800 C., pulverised, and then heated for half an hour at 1000" C. Pigments as described in the following table, and having the structure indicated therein, are obtained.

1.000 gram of Cr O and 2.140 grams of $13 0 are mixed with x g. X +3" g. Sb O heated for half an hour at 800 C., pulverised, and then heated for another half a hour at 1000 C., with results as shown in the following table:

No. 1 g. X y g. Colour Added X-ray SD20; compound structure a- 005g L120- 1.624 Greyish L1Sb30s.-- Trirutlle not tinged well crysgreen. stallised. b 0.50 g. -IgO- 4.010 Medium grey- MgSbrOn- Do. 'c 0.50 g. Z110- 1.987 Greyish ZnSb2O0-- Do.

tinged 7 green. d. 0.50 g. FeO 2.252 Greenish FeSbrOQ Do.

tinged grey. 0.50 g. 000. 2.160 Greyish green- 00813205.- Do. 1 0.50 g. N10- 2.160 Medium NiSb2Ou-- Do.

greenish grey. g 0.50 g. CuO- 2.030 Light green--. CuSb2Oe D0. 11---- 0.5g g.0 0.863 .Greyish green- GaSbO4 Do.

a: a. 1- 0.50 g. VOs- 0.889 Darkish olive- VSbO4 D0.

EXAMPLE 186 1.000 gram of Fe O 2.020 grams of Sb O x g. X and x g. X, y g. Y and z g. S550 are mixed together, heated for half an hour at 800 C., .pulverised, and heated for a further half hour at 1000 C. Pigments witha trirutile structure are obtained, as indicated in the table.

x g. X, y g. Y and 1 g. Sb O are mixed together, heated No. a: g. X y g. Y 2 g. Colour X-ray Sb205 structure a-- 0.50 g. ZnO. 0.50 g. FeQ.- 4.239 Pale greyish Trirutlle.

brown. do- 0.50 g. 000.- 4. 147 Brownish grey D0. 0.50 g. Ni0-- 4. 147 Greenish grey Do. 0.50 g. 0110. 4.017 Green tinged Do.

with grey.

EXAMPLE 190 x g. X, y g. Y and 2 g. Sb O are mixed together, heated for half an hour at 800 C., pulverised and then heated for another half hour at 1000 C. Pigments as set out in the following table are obtained, these pigments having the crystal structure indicated thereini y g. Sb O are mixed, heated for half an hour at 800 C., N v Y C 1 v pulverised, and then heated for another half hour at I i $53 1000 C. Pigments with the crystal structure indicated In the followmg tablefim Obtained: a-- 050g. FeO- 0.50g 000-- 4.412 Brown Trirutile.

. 1).... .do .0.50g.Ni 4.412 Medium Do. No zg.X 1 1g. Colour Added X-ray ggy sbzo mmpmmd Structure c do 050g. 0110- 4. 287 Light grey Do. d 0.50g. 000.. 050g.NiO 4.320 Greyish yel- Do. in 805g lB3eige yelfiwn llwaslhpsn Trirgtlle. gggg g igep' g 2 7 d 050 000 4 190 B i e D 0--.. 0.50g 2110 1.987 Beige yell0w ZnSb200 D0. 0.... 0.50g FeO 2.252 Medium Fashion" D0. Lght grey-m 0 o o 2100 e ii o SbO D .5 0. e ifiitif f EXAMPLE 191 L--. 0.50 g. 10.- 2.160 gllligsgrs 7 1S 2 a-.- o. x g y g 2 5, 2 g Z and a g z s are mixed 0. 03- 0110 2-030 11 e g ged CuShz0e 7 Do. together heated for half an hour at 800" C., pulverised 1.... 050 0310. 0. sea "eg ebrwm. GaSbOr--. Trlrg ijle or nd then heated fgr anoltlheri half hour at11000 Piglments as in icate in t e o owirv ta e are 0 taine 1---- 0.50 .VO- 0.889 D k enih VSbO Tnrutle. 7 g 2 5 3 2.5" s 4 1 these pigments havmg the structure indicated therein. 11.... 0.50g.Or Oa 1.070 Medium yel- CISbOr--- Trirutile 0r lowish rutile. brown. 40 No. z g. X y g. 2 g. Z a g. Colour X-ray S 05 Tazos structure EXAMPLE 187 x g. X, y g. Y and 2 g. Sb O are mixed together, heated 9 5 'ga g' Yelmwlsh for half an hour at 800 C., pulverised, and heated for b-.. ---do..--- 1.010 0.05 g. 0. 295 Mgdium Do. another half hour at 100010. Pigments with a trirun'le 050% 1 070 g? M96 gg g m structure are obtained as set out in the following table: CrzOa NiO do 1. 070 0.0% g(.) 0.307 Greenish grey. Do.

8 No. I g. X r Y 2 a. Colour ay e--- 0.50 g. 1. 987 0.05 g. 0. 27s Grecnish 130.

513205 structure Z110 CuO grayish r d 1 937 001 0 443 W h t D O"..- e o.50 .Lho 0.50 g. MgO- 5.034 Greyishwhite- Trirutile. f 1 e o b 0.50 g. FeOn' 3.876 Page greyish Do.

POWD- c do ZnO 0.50 g 3.611 Yellow tinged Do. 6 d Bwhite. D 7 EXAMPLE 192 (L50 f g x grams X, y grams Sb O and 2 grams SnO are e 0 0. 0 -N 3-784 rmxed together, heated for half an hour at 800 C., pul- 050 GHQ M54 f g D0, verised and then heated. for another half an hour at y 1000 C. Pigments as set out in the following table are obtained, these pigments having the X-ray structure indi- EXAMPLE 188 Gated therein:

No. a: g. X y g. z g. Colour X-ray SbgOs S1101 structure a 1.000 g. A 3. 174 0. 4 17 Greyish white..- Tr(iruti1e) 1,100 b-.-. 1.000 g. F620;... 2. 020 0. 302 Yellowish Trirutile.

. brown. 0---. 1.000 g. 01703-- 2.140 0.314 Whitish grey.-- Do.

--.- 0.500 g. C3103. 0.863 0.136 Greyish white..- Thirutile) 1,100 e- 0.500 g. V20 0. 889 0.139 Blackish brown- Trirutile 0.100 g. Li 0 3. 248 0.335 Whitish grey Do. 3.... 0.500 g. Mg0 4.010 0. 451 do Do. h 0.500 g. ZnO... 1. 987 0. 249 do Do. i 0.500 g. FeO... 2. 252 0.275 Greyish brow-11.- Do. m. 0.500 g. 000... 2.160 0.266 Dark greenish Do.

grey. 1---- 0.500 g. NiO--- 2.160 0.266 Green tinged Trirutile with grey (1,100) m-.- 0.500 g. Ouo--. 2.030 0. 253 Greyish brown 'lrirutile 29 EXAMPLE 193 1.000 gram of ZnO, 3.974 grams of Sb O and 1.000 gram of ZrO (calculated from zirconium nitrate) are mixed together, heated for half an hour at 800 C., pulverised, and then heated for half an hour at 1000 C. A greyish white pigment with a trirutile structure is obtained.

EXAMPLE 194 1.000 gram of A1 0 3.174 grams of 813 0 and 0.500

gram of Ge0 are mixed together, heated for half an hour at 800 C., pulverised, and then heated for another half hour at 1000 C. A dirty white pigment having a disturbed trirutile or rutile structure is obtained.

EXAMPLE 196 1.000 gram of A1 0 3.174 grams of Sb O and 0.500 gram of AlPO are mixed together, heated for half an hour at 800 C., pulverised, and heated for another half hour at 1000 C. A whitish-grey pigment with a disturbed trirutile structure is obtained.

EXAMPLE 197 1.000 gram of CuO, 4.065 grams of Sb O and 1.000 gram of A1AsO are mixed together, heated for half an hour at 800 C., pulverised, and then heated for another half hour at 900 C. A pale grey pigment with a monoclinic trirutile structure is obtained.

EXAMPLE 198 x grams X, y grams Sb O and z grams Z are mixed together, heated for half an hour at 800 C., pulverised, and then heated for half an hour at 1000 C. Pigments as set out in the following table are obtained, these pigments having X-ray structures as indicated therein:

No. I g. X 1! g. 2 g. Z Colour X-rey Sb Oa structure a- 1.000 g. 3 174 0.500 g. Light greeu Trirutile A1203 N 1F: (11S- turbed (1,l00) b do 3. 174 1.000 g. Greyish whiter Do.

Ivl'gF 0-.-. do 3.174 0.500 g. Yellow'ish Do.

C01 grey d 1.000 g. 2.140 1.000 g Pale green Trirutile 01203 MgFz (1,100) e. do- 2.140 0.500 g. Green tinged Trirutile CoF with blue. f 1.000 g. 2.020 1.000 g. Pale red Do.

F6203 MgFz g do 2. 020 1.000 g. Dark olive Do.

MnFg brown EXAMPLE 199 x grams, X, y grams Sb O and 2 grams Z are mixed together, heated for half an hour at 800 C., pulverised, and then heated for half an hour at 1000 C. Pigments as indicated in the following table are obtained, these pigments having crystal structures as set out therein:

30 EXAMPLE 200 1.000 gram of ZnO, 3.974 grams of Sb O and 0.020 gram of Calare mixed together, heated for half an hour at 800 C., pulverised, and then heated for half an hour at 1000 C. A greyish pigment having a trirutile structure is obtained.

EXAMPLE 201 2.000 grams of E6 0 4.040 grams of Sb O and 0.500 gram of CaF are mixed together, heated for half an hour at 800 C., pulverised, and then heated for half an hour at 1000 C. A medium brown pigment with a trirutile structure is obtained.

EXAMPLE 202 1.000 gram of ZnO, 3.974 of Sb O and 0.500 gram of CdF are mixed together, heated for half an hour at 800 C., pulverised, and then heated for another half hour at 1000 C. A grayish-white pigment with a yellowish tinge and having a somewhat disturbed trirutile structure is obtained.

EXAMPLE 203 1.000 gram of A1 0 (calculated from A1(OH) and 3.174 grams of 811 0 are mixed with x grams X and y grams LiF, heated for half an hour at 800 C., pulverised and then heated for half an hour at 1000 C. Pigments as set out in the following table are obtained, these pigments having X-ray structures, as indicated therein:

No. 2 g. X y g. Colour X-ray LiF structure a 0.500 g AlF3 0.155 White Trirutile. b 0.500 g FeFa 0.115 Grey tinged with Do.

yellow. 0..... 0.500 g CrF; 0.119 Wliitish yellow Do.

-. 0.500 g GaF3 0.102 White Do.

EXAMPLE 204 1.000 gram of Fe O 2.020 grams of $13 0 x grams X and y grams LiF are mixed together, heated for half an hour at 800 C., pulverised, and then heated for another half hour at 1000 C. Pigments as set out in the following table are obtained, these pigments having crystal structures as indicated therein:

1.000 gram of ZnO, 3.974 grams of 815 0 x grams X and y grams LiF are mixed together, heated for half an hour at 800 C., pulverised, and then heated for another half hour at 1000 C. Pigments as set out in the following table are obtained, these pigments having X-ray structures as indicated therein:

No. x g. X y g. Colour X-ray LrF structure a. 0.500 g. AlF3 0.155 WIhite tinged with yel- Trirutile.

b 0.500 g. CrFav 0.115 Greyish brown Do.

c 0.500 g. FeFrn 0.119 Light beige Do.

d 0.500 g. GaF3- 0.102 ite Do.

EXAMPLE 206 1.000 gram of Cr O 2.140 grams oi $17 0 x grams 31 X and y grams Li O (calculated from Li CO are mixed together, heated for half an hour at 800 (3., pulverised and then heated for another halfhour at 1000 C. Pigments as indicated in the following table are obtained, these pigments having crystal structures as indicated therein: t

No. 2 g. X y g. Colour X-ray structure Lizo a 0.250 g. AIF3 0. 02% Dirty green Trirutile. be-" 0.250 g. (Jr-F3" 0. 0228 Greyish green Trimtile disturbed. o"... 0.250 g. FeF3 0.0220 Greenish g1'ey D d 0.250 g. GaFs- 0.0196 Greyish green-" Do.

EXAMPLE 207 1.000 gram of C00 and 4.432 grams of Sb O are mixed with x grams X and 31 grams Li O (calculated from Li CO heated for half an hour at 800 C., pulverised and then heated for another half hour at 1000 C. Pigments as described inv the. following table are obtained, these pigments having structures as set out therein:

No. x g. X y g. Colour X-ray struc- Li20 ture 2..---- 0.500 g. AlFan 0. 0592 Greyish green Trirutile. b 0.500 g. CrFa 0. 0456 Greyish green tinged Do.

with brown. 0"... 0.500 g. Fem 0.044 Brown tinged with olive, 130.. d--- 0.500 g. 0.11%.. 0. 0392 Green tinged with grey- Do.

EXAMPLE 208 1.000 gram of A1 0 3.174 grams of So O x grams X and y grams Y are mixed together, heated for half an hour at 800 C., pulverised, and then heated for another half hour at 1000 C. Pigments as set out in the following table are obtained, these pigments having X-ray structures as indicated therein:

No. :c g. X y g. Y Colour X-ray structure a..... 0.500 g. AlFan 0.446 g. C00,- Light blue Tr i rutils turbed. b t do 0.240 g. Mg0 Whitish grey 0. c do 0.422 g. Mn0 Browntinged with Trirutile.

7 yellow. d do 0.428 g. FeO-.. Yellowish beige Do. e do 0.474 g. CuO Greyish pink Do.

. EXAMPLE 209 0.500 gram of MgO, 4.010 grams of Sb O x grams X and y grams Y are mixed together, heated for half an hour at 800 C., pulverised, and then heated for another half hour at 1000 C. Pigments as set out in the following table are obtained, these pigments having crystal structures as mentioned therein:

No. I g. X y g. Y Colour X-ray structure a. 0.500 g. CIFa 0.344 g. CoO Greyish green..- Trirutile.

o 0.343 g. NiO- Gil aelen tinged with Do.

us. 0 d0 0.325 g. MnO Light-brown Do. d -do 0.330 g. FeO.-. -do Do.

. EXAMPLE 210 i 1.000 gram of A1 0 3.174 grams of $17 0 17 grams X and y grams Y are mixed together, heated for hflf 'an hour at 800 C., pulverised, and then heated for another half hour at 1000 'C. Pigments as set out in 32 the following table are obtained, these pigmentshaving the X-ray structures indicated therein: a

No a: g. X y g. Y Colour X-ray structure 8...--- 0.250 g. AlFs- 0.475 g. F8203- Light-grey- Trirutile disturbed(1,l00). b 0.250 g. FeF3 0.226 g. A1203" Trirutile disturoed. c.- 0.250 g. CrF 0.234 g. A1203 Trirutile disturbed (1.100) d-- do 0.366 g; FezOs. Trirutile disturbed.

. EXAMPLE 211 0.100 gram of Li O (calculated from Li CO and 3.248 grams of 513 0 are mixed with 1: grams MeF and y grams Y, heated for half an hour at 800 C. pulverised and then heated for another half hour at 1000 C. Pigments as indicated in the following table are obtained, these pigments having the structures set an hour at 700 0.500 gram of Ni(), 2.160 grams of 817 0 x grams X and y grams LiF, are mixed together, heated for half an hour at 800 C., pulverised, and then heated for another half hour at 1000 C. Pigments as set out in the following table are obtained, these pigments having the crystal structures indicated therein:

No. a: g. X 1/ g. Colour X-ray structure LiF 0. 0130 Bluish green Trirutile disturbed. 0. 0244 Greyish green- Triturile somewhat disturbed. 0. 0357 Olive green. Trirutile. 0. 0147 Bluish grey D0.

EXAMPLE 213 1.000 grams of Ga O 1.726 grams of 517 0 x grams X and y grams LiF are mixed together, heated for half an hour at 800 C. pulverised, and then heated for another half hour at 1000 C. Pigments as set out in the following table are obtained, these pigments having the X-ray crystal structures indicated therein:

No. x g. X 11 g. Colour X-ray structure LiF 0.250g. M003- 0. 0451 Light grey. Trirutile.

0.250 g. W03" 0.0280 White 130.

0.250 g. U03"- 0.0227 Greem'sh grey- Trirutile somewhat disturbed. 0.250 g. Te0a 0.0369 Yellfiivtvish Trirutile very good.

w e. e

In the case of M003, the heating was carried out for half C., and for another half an hour at7800 0., after pulverisation, on account of its volatility.

EXAMPLE 214 1.000 gram of A1 0 and 3.174 grams of 813 0 are mixed with 0.500 gram of C00, 1.546 grams of D0 and 0.200 gram of NaF, heated for half an hour at 800 C., pulverised, and then heated for another half hour at 1000 C. A grey pigment with a greenish tinge is obtained, this pigment having a trirutile structure.

EXAMPLE 2 l 5 1.000 gram of A1 0 3.174 grams of sb og, 0.500 gram of ZnO, 1.425 grams of W0 and 0.200 gram of 33 NaF are mixed together, heated for half an hour at 800 C., pulverised, and then heated for another half hour at 1000 C. A grayish white pigment is obtained, this pigment having a disturbed trirutile structure.

EXAMPLE 216 1.000 gram of A1 3.174 grams of Sb O 0.500 gram of N and 1.915 grams of U0 are mixed together, heated for half an hour at 800 C., pulverised, and then heated for another half hour at 1000" C. A greyish green pigment having a disturbed trirutile structure is obtained.

EXAMPLE 2 17 1.000 gram of A1 0 and 3.174 grams of Sb O 0.050 gram of M 0 and 0.722 gram of M00 are mixed together, heated for half an hour at 700 C., pulverised, and then heated for another half hour at 800 C. A greenish-grey pigment which has a disturbed trirutile structure is obtained.

EXAMPLE 21 8 1.000 gram of A1 0 3.174 grams of Sb O 0.500 gram of Fe O and 0.726 gram of W0 are mixed together, heated for half an hour at 800 C., pulverised, and then heated for another half hour at 1000 C. A greyish-olive green pigment is obtained, this pigment having a finely divided trirutile structure.

EXAMPLE 219 0.100 gram of Al O +0.3l7 gram of Sb O +0.100 gram of Fe O +0202 gram of Sb O +0.100 gram of Cr O +02l4 gram of Sb O +0.050 gram of Li O+1.624 grams of Sb O +0.050 gram of ZnO-[0.198 gram of Sb O +0.050 gram of NiO+0.216 gram of Sb O +0.050 gram of CuO+0.203 gram of Sb G +0500 gram of MgF +0200 gram of LiF+0.087 gram of AlF +0.200 gram of CrF +0.0183 gram of Li O+0.250 gram of AlF +0.223 gram of C00+0.100 gram of AlF +0.18l gram of Cr O +0.200 gram of Nb O +0.0195 gram of LiF+0.300 gram of WO +0.336 gram of LiF are mixed together, heated for half an hour at 800 C., pulverised, and then heated for another half hour at 1000 C. A brown pigment with an olive tinge is obtained, this pigment having a trirutile structure.

I claim:

1. Solid solutions consisting of rutile lattice forming compounds selected from the group consisting of TiO SD02, ,B'MBOz, P1302, V02, Geog, TCOg, CI'OZ, R1102, 0e0 irO MgF ZnF MnF FeF CoF NiF PdF LiSb O MgSb O 211513 0 FeSb O COSbzO NiSb O CuSb O AlSbCu, GaSbO VSbO CrSbO FeSbO RhSbO MgTa205, NlTfizOe, CoTa O FBTfizO CITaOr FeTaO RhTaO CrNbO FeNbO RhNbO and RhVO and additional compounds selected from the group consisting of 2-valent metal fluorides, 1-, 2- and 3-valent metal oxides and fluorides, 5- and 6-valen-t metal oxides, mixtures thereof and mixtures of 2-valent metal fluorides, 1-, 2- and 3-valent metal oxides and fluorides and 5- and 6-Valent metal oxides with 4-valent metal oxides, the cations of said additional compounds possess radii between 0.46 A. and 0.91 A., and said additional compounds being present in such proportions, relatively to one another, that the ratio of the sum of their cations to the sum of their anions is 1:2 (512%) while preserving statistical electroneutrality in the lattice.

2. Solid solutions according to claim 1, wherein the total amount of the additional components is not greater than the total amount of rutile lattice forming components.

3. Solid solutions according to claim 2, wherein the total content of the additional components is between about 0.5 and about percent by weight.

4. Solid solutions according to claim 1, wherein the rutile lattice forming component is titanium dioxide.

5. Solid solutions according to claim 1, wherein the rutile lattice forming component is tin dioxide.

6. Solid solutions according to claim 1, wherein the rutile lattice forming component is selected from the group consisting of an antimonate, niobate, tantalate and vanadate.

7. A process for the production of solid solutions according to claim 1, wherein the rutile lattice forming components are heated from 1 to 3 hours with the addi tional components at temperatures of about 600-1350 C. so as to form the solid solutions.

8. Solid solutions according to claim 1 wherein the rutile lattice forming compound is T10 and the additional compounds are Cr O and Sb O References Cited in the file of this patent UNITED STATES PATENTS 2,437,171 Pechukas May 2, 1948 2,756,157 Beals et al July 24, 1956 2,796,358 Foss June 18, 1957 2,875,085 Morris et al Feb. 24, 1959 FOREIGN PATENTS 384,473 Great Britain Dec. 8, 1932 448,345 Great Britain June 8, 1936 472,605 Great Britain Sept. 24, 1937 OTHER REFERENCES Johnson et al.: Journal of the American Ceramic Socity, volume 32, No. 12, 1949, pages 398401.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,022,186 February 20 1962 Franz Hund column 13, lines 3 and 31, for "Cb O each occurrence,

read Sb 0 column 32, second talol e column 2 line 2 thereof, for "GAF read GaF line 67, for "D0 read W0 Signed and sealed this 24th day of July 1962.

(SEAL) Atteat:

ERNEST w. SWIDER DAVID LADD Attesting Officer Commissioner of Patents 

1. SOLID SOLUTIONS CONSISTING OF RUTILE LATTICE FORMING COMPOUNDS SELECTED FROM THE GROUP CONSISTING OF TIO2, SNO2, B-MNO2, PBO2, VO2, GEO2, TEO2, CRO2, RUO2, OSO2, IRO2, MGF2, ZNF2, MNF2, FEF2, COF2, NIF2, PDF2, LISB3O2 MGSB2O6, ZNSB2O6, FESB2O6, COSB2, NISB2O6, CUSB2O6, ALSBO4O6, GABSO4, VSBO4, CRSBO4, FESBO4, RHSBO4, MGTA2O6, NITA2O6, COTA2O6, FETA2O6, CRTAO4, FETAO4, RHATO4, CRNBO4, CRNBO6, FENBO4, RHNBO4 AND RHVO4, AND ADDITIONAL COMPOUNDS SELECTED FROM THE GROUP CONSISTING OF 2-VALENT METAL FLUORIDES, 1-, 2- AND 3-VALENT METAL OXIDES AND FLUORIDES, 5- AND 6-VALENT METAL OXIDES, MIXTURES THEREOF AND MIXTURES OF 2-VALENT METAL FLUORIDES, 1-, 2- AND 3-VALENT METAL OXIDES AND FLUORIDES AND 5- AND 6-VALENT METAL OXIDES WITH 4-VALENT METAL OXIDES, THE CATIONS OF SAID ADDITIONAL COMPOUNDS POSSESS RADII BETWEEN 0.46 A. AND 0.91 A., AND SAID ADDITIONAL COMPOUNDS BEING PRESENT IN SUCH PROPORTIONS, RELATIVELY TO ONE ANOTHER, THAT THE RATIO OF THE SUM OF THEIR CATIONS TO THE SUM OF THEIR ANIONS IS 1:2 ($2%) WHILE PRESERVING STATISTICAL ELECTRONEUTRALITY IN THE LATTICE. 